Triboluminescence and X-Rays

T. V. Prevenslik Consultant, Discovery Bay, Hong Kong, China [email protected]

ABSTRACT: Triboluminescence is shown to may be observed if you chew fresh, dry produce X-rays from the nanoparticles (NPs) that Wint-O-Green candies in a dark room -- or snap them form as the sticky acrylic adhesive of Scotch tape is in two using a pair of pliers -- you see a spark of peeled from the polyethylene (PE) roll in a vacuum. visible (VIS) light having a green/blue color. But how Prior to peeling, atoms in the adhesive are not under this occurs is debated to this day. electromagnetic (EM) confinement and have full It is commonly thought [1] the VIS light from thermal kT energy. But upon peeling, the atoms in crushing “Life Savers” is caused by the collision of NPs that form in the gap between adhesive and PE electrons with nitrogen in the air because are under EM confinement at vacuum excited nitrogen is known to emit green/blue VIS (VUV) frequencies that by quantum mechanics (QM) light. But this is unlikely because electrons cannot be are restricted to vanishing kT energy. Momentarily, removed from atoms by crushing. Einstein showed the NP atoms therefore have kT energy in excess of with the photoelectric effect that EM and not that allowed by QM. But the specific heat of NPs at VUV frequencies also vanishes, and therefore the mechanical energy is required to free an electron from excess kT energy cannot be conserved by an increase an atom. The electron is bound to the atom far tighter in temperature. Since the NPs have EM confinement than the atoms are bound to each other, and therefore frequencies at VUV levels, and since the lowest crushing cannot excite the electrons to produce the frequency allowed in the NP is at its EM frequency, VIS light upon collision with nitrogen. the low frequency kT energy is frequency Instead, crushing is likely to only form particles of up-converted to VUV levels by quantum neutral clusters of atoms. Given that VIS light is electrodynamics (QED). Conservation then proceeds observed on crushing, it can only be concluded that the by a burst of VUV radiation that by the photoelectric particles that form somehow produce EM radiations at effect charges the adhesive positive while the the VUV levels necessary to excite nitrogen. liberated electrons charge the PE negative. Charge Another explanation for the VIS light in crushing accumulates during peeling by the VUV radiation “Life Savers” is fluorescent that from a continual supply of NPs until the breakdown gives you the flavor of wintergreen oil. of voltage is reached across the gap between the means VUV light is absorbed and then is emitted as adhesive and the PE. Electrons from the PE then 8 light of a longer wavelength which for methyl are accelerated to velocities of about 10 m/s in gaps salicylate is similar to the VIS light from nitrogen. Of up to 1000 microns. Upon collision with the adhesive, importance is not the emission of VIS light from any electron bremstraahlung produces x-rays from 15 to specific chemical species, but rather that VUV 100 keV. radiation is somehow produced in particles.

KEYWORDS: Triboluminescence, tape, x-rays VUV radiation from particles is similar to that produced by QED induced EM radiation [3]. But not I. TRIBOLOLUMINESCENCE all particles produce EM radiation at the VUV levels necessary to excite chemical species. Only NPs do so.

Micron particles (MPs) are induced by QED to emit in Wikipedia explains the light emission in the infrared (IR), but chemical species are generally triboluminescence: "electrical fields are created; not excited with IR radiation. separating positive and negative charges that then create sparks while trying to reunite." The light emission is thought [1] to occur as crystalline II. X-RAYS IN TRIBOLOGY materials are scratched, crushed or rubbed. The name triboluminescence comes from the Greek tribein ("to In 1930, x-rays from triboluminescence were first rub") and the Latin lumen ("light"). Observations of reported [4] by Obreimoff. Splitting of mica by a light emission have a long history. In 1620, Francis wedge in an evacuated glass vessel under 1 – 0.1 mm Bacon in Novum Organum stated: mercury vacuum produced x-rays similar to a Geissler tube. Only VIS light was observed by splitting mica at "It is almost certain that all sugar, whether refined atmospheric pressure. or raw, provided only it be somewhat hard, sparkles Triboluminescence in mica and adhesive tape [5] when broken or scraped with a knife in the dark." were observed in 1939 by Harvey:

“It is not possible to prove that mica sheets or tire tape, “It is not possible to prove that mica sheets …or Scotch surgeons’ tape or Scotch tape are oppositely charged as tape are oppositely charged as a whole when pulled apart.” a whole when pulled apart, but there are no doubts local positive and negative regions developed, the discharge Tribocharging by accumulated charge is suggested between them giving rise to ”. because of the nanosecond x-ray bursts observed in Triboluminescence without x-rays in the peeling of peeling Scotch tape. tape was studied by many researchers. Seminal work Recently, McCarty et al. proposed [11] a theory of by Dickenson, et al. included bursts of light having contact electrification based on ion transfer making nanosecond duration [6] in 1988 and measurement of the undeniable argument that to transfer an electron current flow [7] from tape peeled from metal surfaces from nylon in contact with PE requires energies of in 1995. Also Miura et al. in 1997 correlated [8] the 5-10 eV while the available kT energy of atoms at electrical discharge with the fracture of adhesive ambient temperature is only 0.0258 eV. However, filaments in tape. In these seminal works any x-rays other electron transfer mechanisms were not that accompanied the observed triboluminescence considered. from peeling tape were not reported. In this paper, tribological charging is based on the In this regard, it is worthwhile to note that x-rays electron transfer by QED induced EM radiation [3] were discovered [9] by Röntgen in 1895 while applicable to a wide range of tribology including experimenting with the cathode ray tube (CRT). CRTs peeling Scotch tape, splitting mica, and crushing “Life are devices which the positive anode attracts electrons Savers.” By this theory, the 5-10 eV necessary to from the negative cathode in a vacuum. The electrons remove electrons from nylon cited by McCarty et al. only requires the formation of NPs upon rubbing upon collision with the anode emit x-rays by bremstraahlung. against PE. Any ion transfer is likely insignificant. Recently, x-rays were reported [10] by Camara, et Applications of QED induced EM radiation in tribology are limitless, and to cite a few: al., at UCLA by peeling 3M brand Scotch tape at steady 3 cm/s in a vacuum. The tape did not emit Over 2000 years ago, the Greeks discovered static x-rays continuously, but in short nanosecond bursts – electricity upon rubbing an amber rod with a cloth. accumulating enough energy to produce an x-ray QED induced EM radiation [12] explains the image of a finger in a second. Most brands of clear charging by the amber NPs that form upon rubbing. adhesive tape also give off x-rays, albeit with a Numerous observations [3] of photons and electrons different spectrum of energies, although why duct tape find origin in the formation of NPs. Indeed, the does not emit X-rays is not explained. microplasma in tribochemistry [13] having electron emission [14] from a few eV to 1 keV is explained by But how are x-rays produced in splitting mica or peeling tape? photochemistry driven by QED induced EM radiation from NPs that form during the rubbing and scratching Both split mica and peeled tape are similar to the of surfaces. CRT in that a gap forms between the surfaces, so if one surface is charged positive and the other negative, III. THEORY electrons may be accelerated to high velocities. Provided the accumulated charge produces a high X-rays by QED induced EM radiation rely on voltage across the gap, both split mica and peeled VUV emission from NPs to charge the adhesive tape act as a CRT in producing x-rays. The problem positive while the liberated electrons move to the is Röntgen charged the CRT with external voltage electronegative PE. Upon breakdown the PE while the mica and tape must somehow be charged in electrons are accelerated to velocities of about 108 the process by which they are formed. m/s that upon collision with the adhesive are Long–standing tribology holds that charging in decelerated to generate 15 to 100 keV x-rays by peeling tape [10] occurs by the abrupt separation of bremsstrahlung as illustrated in Fig. 1. the sticky adhesive from the PE, the adhesive charged positive with the PE negative charged. However, this X-rays Adhesive is unlikely. For if it was, steady x-rays would be Positive emitted and not the in nanosecond bursts as observed. + Charge Instead, the charging accumulates non-uniformly VUV Electron PE NP on the adhesive from VUV induced from NPs that Electron Negative form as adhesive fractures. In fact, x-ray emission Gap G Charge correlates (Fig.2b of [10]) with the collapse of the stick-slip peeling force. Many local discharges therefore occur that are not uniform over the Fig. 1 X-rays from Scotch Tape separation as a whole. In this regard, Harvey’s Conserving Excess kT Energy by X-ray Emission statement is still applicable. A. QM Restrictions hc QM restricts the kT energy of atoms depending on l the EM confinement wavelength l of the NPs. At 300 U = 3N (2) é æ hc ö ù K, the Einstein-Hopf relation [15] for the harmonic êexpç ÷ -1ú oscillator gives the kT energy as shown in Fig. 2. ë è lkT ø û For the specific heat C given by ¶U/¶T, the 0.1 dimensionless specific heat C* is, kT - eV 0.01 2 avg æ hc ö é hc ù E exp hc ç ÷ ê ú 0.001 C è lkT ø ëlkT û l C* = = (3) Eavg = 2 é æ hc ö ù 3Nk é hc ù 0.0001 êexpç ÷ - 1ú æ ö ë è lkT ø û êexpç ÷ -1ú ë è lkT ø û

Planck Energy - 0.00001 1 10 100 1000 At 300 K, C* vanishes for l = 2nrD < 5 microns. Wavelength - l - microns For nr =1.2, the absorbed EM energy is therefore conserved for D > 2 microns by a temperature

Fig. 2 Harmonic Oscillator at 300 K increase while EM emission occurs for D < 2 In the inset, h is Planck’s constant, and c the speed of light. microns.

Prior to peeling, the atoms in the adhesive are not IV. ANALYSIS under EM confinement and have full kT energy; whereas, the NP atoms under EM confinement have A. NP Charge small kT energy. Fig. 2 shows full kT energy ~ In peeling Scotch tape, the atoms in NPs that 0.0258 eV for l > 100 microns in the FIR and kT ~ -5 form from the adhesive have the same kT energy as 1x10 eV at EM confinement of l ~ 5 microns. that prior to fragmentation. The energy U of a NP is, Hence, NPs under EM confinement at VUV 3 3 p æ D ö p æ D ö wavelengths l < 0.050 microns have vanishing small U = ç ÷ 3kT = ç ÷ kT (4) kT << 1x10-5 eV. 6 è D ø 2 è D ø where, D is the cubic spacing between NP atoms at B. EM Confinement Frequencies density, D ~ 0.3 nm. Lacking specific heat, the For NPs having D << l, the EM confinement is NP conserves the energy U in a burst of VUV analogous [13] to the QM analogy of creating radiation that by Einstein’s photoelectric effect photons of wavelength l by supplying EM energy to electrifies the surroundings. The charge q is, a QM box with walls separated by l/2. For NPs of 3 U æ D ö n r D diameter D and refractive index nr, the EM q = N Ye = Ye = pkTç ÷ Ye (5) P E D hc confinement frequency f and Planck energy EP, P è ø where, NP is the number of QED photons induced in c hc hc the NPs at Planck energy EP. Charging is optimum f = , l = 2n D , and E = = (1) r P for D ~ 100 nm [13]. For the adhesive having nr = 1.2, l l 2n r D l = 240 nm and EP > 5 eV where most materials [16] have yields Y ˜ 0.1 electrons/VUV photon. Here, C. Vanishing Specific Heat each NP is taken to produce charge q ˜ 4.8 fC / NP. Classical heat transfer conserves absorbed EM energy by an increase in temperature, but is not B. NPs and Electrical Voltage and Field applicable to NPs because of the QM restrictions on For NPs that form in the gap G between the thermal kT energy. Equivalently, the specific heat of adhesive and PE, the voltage V and field F, NPs vanishes. But the Einstein specific heat for the NP atoms as harmonic oscillators is modified for thermal qN np V photons under EM confinement. V = and F = (6) Einstein assumed the atoms in are harmonic 4peo G G oscillators vibrating independent of each other. But where, Nnp is the number of NPs that form and G is the thermal photons as oscillators vibrate not only the gap. coherently at the EM confinement frequency having Electrical breakdown for the adhesive depends on the shape of a spherical box of photons, but at optical the surface asperities and is not known. The typical breakdown field F in a vacuum [17] is about 2.5x107 instead of atomic frequencies. Taking one thermal V/m that is bracketed here by F = 108 V/m. Fig. 3 photon for each degree of freedom, the energy U of a shows breakdown voltage V and the number Nnp of NP with N atoms, 100 nm NPs necessary for a given gap G. For G = 150 and 300 microns, V = 15 an 30 keV with Nnp = 46,000 and 184,000, respectively. C. Rate and Number of NPs for Breakdown NP diameters less than 100 nm have the necessary The number Nnp of NPs produced in the peeling of EM confinement to induce VUV radiation. Scotch tape is not known. An estimate of the rate of The simulation of x-rays is described through NPs necessary to balance the measured X-ray simple calculations based on the production of 100 emission Q is, nm NPs. Smaller NPs and MPs are ignored, although they also will be produced in peeling tape. dN np wv q = Q < kT (7) 2 Experimental data on the number and distribution of dt D NPs is required to complement the x-ray calculations. The spectrum of x-ray energies (Fig. 3 of [10]) during X-rays from Scotch tape and not duct tape is peeling at velocity v = 3 cm/s gives Q = 2 nW, and 5 explained by NPs less than 100 nm that produce therefore dNnp/dt ˜ 4.16x10 /s. This is reasonable VUV radiation are more likely to form in the thin provided Q is a small fraction of the rate of kT energy Scotch tape while MPs are likely to form in duct tape. available in the adhesive surface atoms. For tape The generality of QED induced EM radiation not width w = 20 cm, Q is upper bound by 2.76x10-5 W -5 only allows x-rays to be inherent in tribology but that so Q is about 10 of the available surface kT energy. all of electrostatics may be unified through NPs, e.g., static electricity from NPs that form in rubbing of

100000 10000000 solids, and atmospheric electricity from ice NPs that form from frosted surfaces of upward moving water 1000000 droplets in the draft of a thunderstorm.

Nnp 100000 REFERENCES [1] Oullette, J., “Cocktail Party Physics,” See of 100 nm NPs.

10000 np http://www.twistedphysics.typepad.com/ [2] Skullsinthestars, “X-rays from Scotch Tape,” See Voltage - V volts http://skullsinthestars.com/2008/11/20/x-rays-from-scotch-t V 1000 ape/ Number N [3] Prevenslik, T., 2008, QED Induced EM Radiation, See 10000 100 http://www.nanoqed.org/ 100 1000 [4] Obreimoff, J.W., 1930, “The splitting strength of mica,” Proc. R. Soc. A, 127, pp. 290-297. Gap - G - microns [5] Harvey, N.E., 1939, “The luminescence of adhesive tape,” Fig. 3 X-rays from Peeling Scotch Tape Science, 89, pp. 460-461. [6] Dickenson, J.T, Zhenyi, M., and Jiawen, F., 1988, “Properties of the Photon emission in the peeling of The number Nnp of NPs necessary for charge to Pressure Sensitive Adhesives,” J. Adhes. , 25, pp. 63. accumulate to breakdown may be estimated from the [7] Dickenson, J.T., Lee, S., Jensen, C., Scudeiro, L., and rise time Dt for the force (Fig. 2b of [10]). Taking Dt Langford, S.C., 1994, “Fracto-emission and electrical 5 transients due to Adhesive Fracture,” J. Adhes. Sci. Tech.., 8, = 0.25 s, Nnp = (dNnp/dt) •Dt ~ 1x10 . Fig. 3 shows the pp. 1286-1309. corresponding breakdown voltage V ~ 23,000 volts at [8] Miura, T., Chini, M., and Bennewitz, R., 2007, “Forces, field F = 108 V/m occurs at gap G ~ 230 microns. charges, and light emission during the rupture of adhesive contacts,” J. App. Phys., 103, pp.103509. [9] Röntgen, W.C., 1895, “On a New King of Rays: translation D. Electron and X-ray Energy of a paper read before the Wurzburg Physical and Medical Conservation of the electron potential energy eV Society,” Nature, 53, pp.274-6. with the kinetic gives its velocity ve, [10] Camara, C.G, Escobar, J.V., Hird, J.R., as Putteman, S., 2008, “Correlation between nanosecond X-ray flashes and v e = 2eV / m (8) stick-slip in peeling tape,” Nature, 455, pp. where, m is the electron mass. For V = 27,000 volts, 1089-1092. 8 [11] McCarty, L. and Whitesides, G.M, 2008, “Electrostatic ve = 1.2x10 m/s. The Planck energy EP of the x-ray charging due to separation of ions at interfaces: contact upon bremstraahlung is, EP = 27 keV. electrification of Ionic electrets,” Angew. Chem. Int. Ed., 47, pp.2188-2207. [12] Prevenslik, T., 2008, “A Unified Theory of Natural V. SUMMARY Electrification”, Proc. of 6th Int. Conf. App. Electrostatics, Shanghai Maritime University, November 3-7, pp. 60-63. X-rays in the peeling of Scotch tape follow the [13] Prevenslik, T. “Tribochemistry by Quantum Mechanics,” World Tribology Council (WTC) IV, Tribochemistry physics of CRTs. The separation gap between the Satellite Forum, Kyoto, September 3-7, 2008. adhesive and PE in a vacuum allows electrons from [14] Nakayama, K., 1992, “Triboemission of electrons, ions, and the PE to be accelerated to high velocities at photons from diamondlike carbon films and generation of electrical breakdown. Upon collision with the tribomicroplasma,” Surf. Coat. Tech., 188-189, pp 599-604. [15] Christy, R.W. and Pytte, A. The Structure of Matter: adhesive, the x-rays are produced by bremstraahlung. Introduction Modern Physics, Benjamin, New York, 1965. The x-ray production relies on electron transfer by [16] Guzhov, A.A. and Y.A. Shuba, 1971, “The Photoemission of the photoelectric effect. The Planck energy at VUV Some Massive Insulators in the Vacuum Ultraviolet,” levels necessary to charge the adhesive by removing Optical Technology, 38, pp. 198-199. [17] Kurrat, M., Giere, S., and Schuman, U., 2003, “Electric electrons is induced from the thermal kT energy of Field design for high –voltage vacuum tubes,” XIIIth Int. atoms in NPs by QED induced EM radiation. Only Sym. High Volt. Eng., Delft University, 25-29 August.